Copper films with a thickness in the nanometer range are required as seed layers for the electrochemical Cu deposition to form multilevel interconnects in ultralarge-scale integrated (ULSI) electronic devices. Continuously shrinking device dimensions and increasing aspect ratios of the dual-damascene structures in the copper-based metallization schemes put ever more stringent requirements on the films with respect to their conformality in nanostructures and thickness homogeneity across large wafers. Due to its intrinsic self-limiting film growth characteristic, atomic layer deposition (ALD) appears appropriate for homogeneously coating complex substrates and to replace conventional physical vapor deposition (PVD) methods beyond the 32 nm technology node. To overcome issues of direct Cu ALD, such as film agglomeration at higher temperatures or reduced step coverage in plasma-based processes, an ALD copper oxide film may be grown under mild processing conditions, while a subsequent reduction step converts it to metallic copper. In this poster, which was presented at the AVS 9th International Conference on Atomic Layer Deposition (ALD 2009), held in Monterey, California from 19 to 22 July 2009, we report detailed film growth studies of ALD copper oxide in the self-limiting regime on SiO2, TaN and Ru. Applications in subsequent electrochemical deposition processes are discussed, comparing Cu plating results on as-deposited PVD Ru as well as with PVD and reduced ALD Cu seed layer.

Copper-based multi-level metallization systems in today’s ultralarge-scale integrated electronic circuits require the fabrication of diffusion barriers and conductive seed layers for the electrochemical metal deposition. Such films of only several nanometers in thickness have to be deposited void-free and conformal in patterned dielectrics. The envisaged further reduction of the geometric dimensions of the interconnect system calls for coating techniques that circumvent the drawbacks of the well-established physical vapor deposition. The atomic layer deposition method (ALD) allows depositing films on the nanometer scale conformally both on three-dimensional objects as well as on large-area substrates. The present work therefore is concerned with the development of an ALD process to grow copper oxide films based on the metal-organic precursor bis(tri-n-butylphosphane)copper(I)acetylacetonate [(nBu3P)2Cu(acac)]. This liquid, non-fluorinated β-diketonate is brought to react with a mixture of water vapor and oxygen at temperatures from 100 to 160°C. Typical ALD-like growth behavior arises between 100 and 130°C, depending on the respective substrate used. On tantalum nitride and silicon dioxide substrates, smooth films and self-saturating film growth, typical for ALD, are obtained. On ruthenium substrates, positive deposition results are obtained as well. However, a considerable intermixing of the ALD copper oxide with the underlying films takes place. Tantalum substrates lead to a fast self-decomposition of the copper precursor. As a consequence, isolated nuclei or larger particles are always obtained together with continuous films. The copper oxide films grown by ALD can be reduced to copper by vapor-phase processes. If formic acid is used as the reducing agent, these processes can already be carried out at similar temperatures as the ALD, so that agglomeration of the films is largely avoided. Also for an integration with subsequent electrochemical copper deposition, the combination of ALD copper and ruthenium proves advantageous, especially with respect to the quality of the electroplated films and their filling behavior in interconnect structures. Furthermore, the ALD process developed also bears potential for an integration with carbon nanotubes. / Kupferbasierte Mehrlagenmetallisierungssysteme in heutigen hochintegrierten elektronischen Schaltkreisen erfordern die Herstellung von Diffusionsbarrieren und leitfähigen Keimschichten für die galvanische Metallabscheidung. Diese Schichten von nur wenigen Nanometern Dicke müssen konform und fehlerfrei in strukturierten Dielektrika abgeschieden werden. Die sich abzeichnende weitere Verkleinerung der geometrischen Dimensionen des Leitbahnsystems erfordert Beschichtungstechnologien, die vorhandene Nachteile der bisher etablierten Physikalischen Dampfphasenabscheidung beheben. Die Methode der Atomlagenabscheidung (ALD) ermöglicht es, Schichten im Nanometerbereich sowohl auf dreidimensional strukturierten Objekten als auch auf großflächigen Substraten gleichmäßig herzustellen. Die vorliegende Arbeit befasst sich daher mit der Entwicklung eines ALD-Prozesses zur Abscheidung von Kupferoxidschichten, ausgehend von der metallorganischen Vorstufe Bis(tri-n-butylphosphan)kupfer(I)acetylacetonat [(nBu3P)2Cu(acac)]. Dieses flüssige, nichtfluorierte β-Diketonat wird bei Temperaturen zwischen 100 und 160°C mit einer Mischung aus Wasserdampf und Sauerstoff zur Reaktion gebracht. ALD-typisches Schichtwachstum stellt sich in Abhängigkeit des gewählten Substrats zwischen 100 und 130°C ein. Auf Tantalnitrid- und Siliziumdioxidsubstraten werden dabei sehr glatte Schichten bei gesättigtem Wachstumsverhalten erhalten. Auch auf Rutheniumsubstraten werden gute Abscheideergebnisse erzielt, jedoch kommt es hier zu einer merklichen Durchmischung des ALD-Kupferoxids mit dem Untergrund. Tantalsubstrate führen zu einer schnellen Selbstzersetzung des Kupferprecursors, in dessen Folge neben geschlossenen Schichten während der ALD auch immer isolierte Keime oder größere Partikel erhalten werden. Die mittels ALD gewachsenen Kupferoxidschichten können in Gasphasenprozessen zu Kupfer reduziert werden. Wird Ameisensäure als Reduktionsmittel genutzt, können diese Prozesse bereits bei ähnlichen Temperaturen wie die ALD durchgeführt werden, so dass Agglomeration der Schichten weitgehend verhindert wird. Als besonders vorteilhaft für die Ameisensäure-Reduktion erweisen sich Rutheniumsubstrate. Auch für eine Integration mit nachfolgenden Galvanikprozessen zur Abscheidung von Kupfer zeigen sich Vorteile der Kombination ALD-Kupfer/Ruthenium, insbesondere hinsichtlich der Qualität der erhaltenen galvanischen Schichten und deren Füllverhalten in Leitbahnstrukturen. Der entwickelte ALD-Prozess besitzt darüber hinaus Potential zur Integration mit Kohlenstoffnanoröhren.

Made available in DSpace on 2017-07-10T18:07:59Z (GMT). No. of bitstreams: 1 Alvaro Cesar Dias Alves.pdf: 1860253 bytes, checksum: fce25e3199fa4e1f2d24f3500c996153 (MD5) Previous issue date: 2012-02-24 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / This study aimed to evaluate the efficiency of the process of coagulation/ flocculation and coagulation/flocculation/adsorption combined process for treatment of liquid effluent from the electroplanting industry. Were used the moringa seed as a natural coagulant agent and moringa bark and string bean as adsorbents. Were evaluated the parameters COD, color, pH, turbidity and the concentration of metal ions Cr, Zn, Cu and Ni. In the stage of coagulation/ flocculation were used several concentrations of moringa in salt solution of NaCl 1 M and 0.1M. In the stage of the combined adsorbents were used moringa bark and string beans to determine which of the adsorbent had a better removal efficiency of metals. Tests were also conducted with different ranges of mass for the best adsorbent and variation of pH of the studied effluent. Tests of coagulation/flocculation showed good removal efficiency for the parameters COD, Color, Turbidity and the metals Cr, Zn, Cu and Ni using MO seed in salt solution 1M, these values being 90.49%, 78.34%, 95.13%, 25.29%, 84.30%, 51.11% and 24.74% respectively. In the tests of coagulation/flocculation/adsorption the maximum removal efficiencies were 91.41% for COD, 90.77% for color, 95.31% for Turbidity, 58.36% for Cr, 98.36% for Zn, 97,58% for Cu and 99.11% for Ni. The research showed that after the combined process the electroplanting effluent did not present the necessary characteristics for the released in to water bodies due to the high remaining concentration of Cr (1907.4 mg/L), Color (860 PtCo/L) and COD (330 mg/L). The research for the treatment process demonstrated great effectiveness for most parameters analyzed, however, its necessary to study complementary technologies for this type of treatment effluent in order to achieve an effluent within the release standards into the water bodies. / Este trabalho teve como objetivo avaliar a eficiência do processo de coagulação/floculação e do processo combinado de coagulação/floculação/adsorção para tratamento de efluente liquido da indústria galvânica. Foi utilizada a semente de moringa como coagulante natural e a casca e a vagem de moringa como adsorventes. Foram avaliados os parâmetros DQO, Cor, pH, Turbidez e a concentração dos íons metálicos Cr, Zn, Cu e Ni. Na etapa de coagulação/floculação foram utilizadas várias concentrações de moringa em solução salina de NaCl 1M e 0,1M. Na etapa do processo combinado foram utilizados os adsorventes casca e vagem de moringa para determinação do adsorvente com melhor eficiência de remoção dos metais. Também foram realizados ensaios com variação de massa do melhor adsorvente e variação do pH do efluente estudado. Os ensaios de coagulação/floculação mostraram boa eficiência de remoção dos parâmetros DQO, Cor, Turbidez e dos metais Cr, Zn, Cu e Ni utilizando semente de MO em solução salina 1M, sendo esses valores 90,49%, 78,34%, 95,13%, 25,29%, 84,30%, 51,11% e 24,74%, respectivamente. Nos ensaios de coagulação/floculação/adsorção as eficiências máximas de remoção foram 91,41% para DQO, 90,77% para Cor, 95,31% para Turbidez, 58,36% para Cr, 98,36% para Zn, 97,58% para Cu e 99,11% para Ni. Verificou-se que após o processo combinado o efluente galvânico não apresentou as características necessárias para lançamento em corpos hídricos em função da alta concentração remanescente de Cr (1907,4 mg/L), Cor (860 PtCo/L) e DQO (330 mg/L). Verificou-se que os processos de tratamento estudados demonstraram eficiência para a maioria dos parâmetros analisados, entretanto, fazem-se necessários estudar tecnologias complementares para o tratamento deste tipo de efluente com intuito de obter um efluente dentro dos padrões de lançamentos em corpos receptores.

The present masters's thesis informs about the development and application of low-temperature sintering pastes in the manufacture and assembly of PCB components of the enclosing lead-free using nanoparticles of metals and their compounds. Lead-free brazing technology which s using in the present time, which has its drawbacks, however, and thus gaining other appropriate alternatives that seek to replace or further refined lead brazing. The introduction of the theoretical part inform about retrieval method of the type, composition and properties of low-temperature sintering pastes consisting of metal nanoparticles and their compounds. This section describes and explains the reaction mechanisms taking place during the sintering process. The end of the first chapter is dedicated to nanotechnology and production of nanoparticles and their compounds for the needs of the low-temperature sintering and possible related problems. Folowing section is devoted to examples of practitioners of the application and use of low-temperature sintering pastes and tests with which to assess the characteristics and quality of the related sintering conection. At the end of the thesis is a summary perspective and the use of low-temperature sintering technology nanoparticle past into the future. The experimental part is devoted to the application of conductive ink on the base of graphite for the production of 1V, 2V and 4V structures and their electroplated by the copper. There were created technological processes of 2V and 4V structures and test proposed methodologies resistance conductive theme to environmental influences. Filling pasta was tested in implementing 4V structure. There were made microsections various technological applications and their results were processed and evaluated.

Copper films with a thickness in the nanometer range are required as seed layers for the electrochemical Cu deposition to form multilevel interconnects in ultralarge-scale integrated (ULSI) electronic devices. Continuously shrinking device dimensions and increasing aspect ratios of the dual-damascene structures in the copper-based metallization schemes put ever more stringent requirements on the films with respect to their conformality in nanostructures and thickness homogeneity across large wafers. Due to its intrinsic self-limiting film growth characteristic, atomic layer deposition (ALD) appears appropriate for homogeneously coating complex substrates and to replace conventional physical vapor deposition (PVD) methods beyond the 32 nm technology node. To overcome issues of direct Cu ALD, such as film agglomeration at higher temperatures or reduced step coverage in plasma-based processes, an ALD copper oxide film may be grown under mild processing conditions, while a subsequent reduction step converts it to metallic copper. In this poster, which was presented at the AVS 9th International Conference on Atomic Layer Deposition (ALD 2009), held in Monterey, California from 19 to 22 July 2009, we report detailed film growth studies of ALD copper oxide in the self-limiting regime on SiO2, TaN and Ru. Applications in subsequent electrochemical deposition processes are discussed, comparing Cu plating results on as-deposited PVD Ru as well as with PVD and reduced ALD Cu seed layer.

Copper-based multi-level metallization systems in today’s ultralarge-scale integrated electronic circuits require the fabrication of diffusion barriers and conductive seed layers for the electrochemical metal deposition. Such films of only several nanometers in thickness have to be deposited void-free and conformal in patterned dielectrics. The envisaged further reduction of the geometric dimensions of the interconnect system calls for coating techniques that circumvent the drawbacks of the well-established physical vapor deposition. The atomic layer deposition method (ALD) allows depositing films on the nanometer scale conformally both on three-dimensional objects as well as on large-area substrates. The present work therefore is concerned with the development of an ALD process to grow copper oxide films based on the metal-organic precursor bis(tri-n-butylphosphane)copper(I)acetylacetonate [(nBu3P)2Cu(acac)]. This liquid, non-fluorinated β-diketonate is brought to react with a mixture of water vapor and oxygen at temperatures from 100 to 160°C. Typical ALD-like growth behavior arises between 100 and 130°C, depending on the respective substrate used. On tantalum nitride and silicon dioxide substrates, smooth films and self-saturating film growth, typical for ALD, are obtained. On ruthenium substrates, positive deposition results are obtained as well. However, a considerable intermixing of the ALD copper oxide with the underlying films takes place. Tantalum substrates lead to a fast self-decomposition of the copper precursor. As a consequence, isolated nuclei or larger particles are always obtained together with continuous films. The copper oxide films grown by ALD can be reduced to copper by vapor-phase processes. If formic acid is used as the reducing agent, these processes can already be carried out at similar temperatures as the ALD, so that agglomeration of the films is largely avoided. Also for an integration with subsequent electrochemical copper deposition, the combination of ALD copper and ruthenium proves advantageous, especially with respect to the quality of the electroplated films and their filling behavior in interconnect structures. Furthermore, the ALD process developed also bears potential for an integration with carbon nanotubes. / Kupferbasierte Mehrlagenmetallisierungssysteme in heutigen hochintegrierten elektronischen Schaltkreisen erfordern die Herstellung von Diffusionsbarrieren und leitfähigen Keimschichten für die galvanische Metallabscheidung. Diese Schichten von nur wenigen Nanometern Dicke müssen konform und fehlerfrei in strukturierten Dielektrika abgeschieden werden. Die sich abzeichnende weitere Verkleinerung der geometrischen Dimensionen des Leitbahnsystems erfordert Beschichtungstechnologien, die vorhandene Nachteile der bisher etablierten Physikalischen Dampfphasenabscheidung beheben. Die Methode der Atomlagenabscheidung (ALD) ermöglicht es, Schichten im Nanometerbereich sowohl auf dreidimensional strukturierten Objekten als auch auf großflächigen Substraten gleichmäßig herzustellen. Die vorliegende Arbeit befasst sich daher mit der Entwicklung eines ALD-Prozesses zur Abscheidung von Kupferoxidschichten, ausgehend von der metallorganischen Vorstufe Bis(tri-n-butylphosphan)kupfer(I)acetylacetonat [(nBu3P)2Cu(acac)]. Dieses flüssige, nichtfluorierte β-Diketonat wird bei Temperaturen zwischen 100 und 160°C mit einer Mischung aus Wasserdampf und Sauerstoff zur Reaktion gebracht. ALD-typisches Schichtwachstum stellt sich in Abhängigkeit des gewählten Substrats zwischen 100 und 130°C ein. Auf Tantalnitrid- und Siliziumdioxidsubstraten werden dabei sehr glatte Schichten bei gesättigtem Wachstumsverhalten erhalten. Auch auf Rutheniumsubstraten werden gute Abscheideergebnisse erzielt, jedoch kommt es hier zu einer merklichen Durchmischung des ALD-Kupferoxids mit dem Untergrund. Tantalsubstrate führen zu einer schnellen Selbstzersetzung des Kupferprecursors, in dessen Folge neben geschlossenen Schichten während der ALD auch immer isolierte Keime oder größere Partikel erhalten werden. Die mittels ALD gewachsenen Kupferoxidschichten können in Gasphasenprozessen zu Kupfer reduziert werden. Wird Ameisensäure als Reduktionsmittel genutzt, können diese Prozesse bereits bei ähnlichen Temperaturen wie die ALD durchgeführt werden, so dass Agglomeration der Schichten weitgehend verhindert wird. Als besonders vorteilhaft für die Ameisensäure-Reduktion erweisen sich Rutheniumsubstrate. Auch für eine Integration mit nachfolgenden Galvanikprozessen zur Abscheidung von Kupfer zeigen sich Vorteile der Kombination ALD-Kupfer/Ruthenium, insbesondere hinsichtlich der Qualität der erhaltenen galvanischen Schichten und deren Füllverhalten in Leitbahnstrukturen. Der entwickelte ALD-Prozess besitzt darüber hinaus Potential zur Integration mit Kohlenstoffnanoröhren.